Washing agents, washing adjuvants and cleaning agents containing antimicrobial substances

ABSTRACT

Antimicrobial washing and washing adjuvant preparations comprising (a) from 1 percent to 30 percent by weight of a substituted phenyl ether antimicrobial component of the formula   WHEREIN R1 is a member selected from the group consisting of alkyl having one to four carbon atoms, alkenyl having one to four carbon atoms, haloalkyl having one to four carbon atoms, hydroxyalkyl having one to four carbon atoms and alkoxyalkyl having one to four carbon atoms and R2, R3, R4, R5 and R6 are members selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, halogen, trifluoromethyl, phenyl and nitro and (b) from 99 percent to 70 percent by weight of customary water-soluble components of washing and washing adjuvant preparations, wherein solvents may also be present in addition to components (a) and (b).

[72] Inventors Heinz GunterNosler Monheim Rhineland;

' Harald Schnegelberger, Hilden Rhineland;

I-lorst Belllnger, Dusseldorf; Kurt Rehnelt,

Dusseldorf, all of Germany [21] Appl. No. 743,032 [22] Filed July 8, 1968 [45] Patented Dec. 7, I971 [73] Assignee Henltel & Cie Gmbll Dusseldori-llolthausen, Germany [32] 1 Priorities July 13, 1967 [33] Germany [31 II 63270;

May 9, 1968, Germany, No. P 17 67 426.9

[54] WASHING AGENTS, WASHING ADJUVANTS AND CLEANING AGENTS CONTAINING ANTIMICROBIAL SUBSTANCES 25 Claims, No Drawings [52] U.S. Cl 252/107, 252/ 106 [51] Int.Cl Clld3/48 [50] Field of Search 260/ 106, 107, 612; 424/340, 341

[56] References Cited UNITED STATES PATENTS 2,134,001 10/1938 Mills et a1. 21/5 2,256,612 9/1941 Ellis 260/612 2,289,886 7/1942 Schmerling. 260/621 I 2,615,823 10/1952 Lawloretal l17/138.5

o e f m a Primary Examiner-Leon D. Rosdol Assistant Examiner-P. E. Willis AnorneyHammond & Littell ABSTRACT: Antimicrobial washing and washing adjuvant preparations comprising (a) from 1 percent to 30 percent by weight of a substituted phenyl ether antimicrobial component R5 Ra wherein R is a member selected from the group consisting of alkyl having one to four carbon atoms, alkenyl having one to four carbon atoms, haloalkyl having one to four carbon atoms, hydroxyalkyl having one to four carbon atoms and alkoxyalkyl having one to four carbon atoms and R R R R and R are members selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, halogen, trifluoromethyl, phenyl and nitro and (b) from 99 percent to 70 percent by weight of customary water-soluble components of washing and washing adjuvant preparations, wherein solvents may also be present in addition to components (a) and WASHING AGENTS, WASHING ADJUVANTS AND CLEANING AGENTS CONTAINING ANTIMICROBIAL SUBSTANCES THE PRIOR ART The addition of substances with an antimicrobial action to washing agents is known, especially when the washing agents are to be used under fine washing conditions, that is, at temperatures in the range from 30 to 50 C. These temperatures are not by any means sufiicient to kill unwanted micro-organisms such as bacteria or fungi. The cleaning action of the washing agent must therefore be supplemented by a suitable antimicrobial substance. But an addition of antimicrobial substances may also be desirable in the case of washing agents which are intended for use at higher temperatures, especially in the region of the boiling temperature, especially when the articles to be washed consist of clothing or bed linen from hospitals, where heavy organic contamination, as for example, ointments, blood, pus or sputum, retards the destruction of the micro-organisms. The presence of antimicrobial substances is also frequently desired in the case of cleaning agents which are intended for cleaning other than textile materials in the household, in business and in industry.

OBJECTS OF THE INVENTION An object of the present invention is the obtention of antimicrobial washing and washing adjuvant preparations comprising (a) from I to 30 percent by weight of a substituted phenyl ether antimicrobial component of the formula wherein R, is a member selected from the group consisting of alkyl having one to four carbon atoms, alkenyl having one to four carbon atoms, haloalkyl having one to four carbon atoms, hydroxyalkyl having one to four carbon atoms and alkoxyalkyl having one to four carbon atoms and R R R R, and R, are members selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, halogen, trifluoromethyl, phenyl and nitro and (b) from 99 percent to 70 percent by weight of customary water-soluble components of washing and washing adjuvant preparations, wherein solvents may also be present in addition to components (a) and (b).

A further object of the present invention is the obtention of antimicrobial washing and washing adjuvant preparations comprising (a) from 1 to 30 percent by weight of a substituted phenyl ether antimicrobial component of the formula wherein R, is a member selected from the group consisting of alkyl having one to four carbon atoms, alkenyl having one to four carbon atoms, haloalkyl having one to four carbon atoms hydroxyalkyl having one to four carbon atoms and alkoxyalkyl having one to four carbon atoms and R,, R R R and R, are members selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, halogen, trifluoromethyl, phenyl and nitro, (b) an amount of customary water-soluble complex-forming compounds which, in the Hampshire test, have a complex-forming ability of over 230 mg. of CaCO, per gram of said complex-forming compounds, said component (a) being present in a ratio with respect to component (b) of from 1 to 99 to 50 to 1, and (c) the remainder to I00 parts by weight of the total dry weight of said preparations of customary water-soluble components of washing and washing adjuvant preparations, wherein solvents may also be present in addition to the components (a), (b) and (c).

A yet further object of the present invention is the obtention of antimicrobial washing and washing adjuvant preparations comprising (a) from I to 30 percent by weight of a substituted phenyl ether antimicrobial component of the formula l h R2 wherein R, is a member selected from the group consisting of alkyl having one to four carbon atoms, alkenyl having one to four carbon atoms, alkenyl having one to four carbon atoms, haloalkyl having one to four carbon atoms, hydroxyalkyl having one to four carbon atoms and alkoxyalkyl having one to four carbon atoms and R R R R and R,, are members selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, halogen, trifluoromethyl, phenyl and nitro, (b) at least 5 percent by weight of alkaline-reacting customary builder components which, in the Hampshire test, have a complex-forming ability of not more than 230 mg. of CaCO, per gram, and (c) the remainder to parts by weight of the total dry weight of said preparations of customary water-soluble components of washing and washing adjuvant preparations wherein solvents may also be present in addition to the components (a), (b) and (c).

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The invention relates to washing agents, washing adjuvants and cleaning agents with a content of antimicrobial substances. The preparations according to the invention are characterized by containing (a) l to 30 percent, preferably 2 to 5 percent by weight of a substituted phenyl ether of the general formula in which R, may be a lower aliphatic radical with one to four carbon atoms, which may be substituted by fluorine, chlorine, bromine, iodine or hydroxyl groups or be interrupted by an oxygen atom, and R R R R and R may be hydrogen, fluorine, chlorine, bromine, iodine, the trifluoromethyl radical or another aliphatic radical with one to four carbon atoms, a phenyl or nitro, (b) other usual components of washing agents, washing adjuvants and cleaning agents.

The other usual components of washing and cleaning agents include complex-forming compounds which, in the Hampshire test by the calcium carbonate method, possess a complexing ability of over 230 mg. of CaCO per gram of complex-forming compound. The above antimicrobial substance and the above complex-forming compound may be present in amounts which correspond to a ratio of l to 99 to 50 to l.

The invention further relates to washing agents, washing adjuvants and cleaning agents which contain (a) l to 30 percent, preferably 2 to 5 percent by weight of a substituted phenyl ether of the above constitution, (b) at least 5 percent by weight and preferably at least l0 percent by weight of alkaline-reacting builders customary in such preparations which, in the Hampshire test, have a complex-forming capaci ty corresponding to not more than 230 mg. of CaCO, per gram, (c) if desired, other usual components of washing agents, washing adjuvants or cleaning agents. These mixture components refer to the sum of the quantities of component (a) and the quantities of the water-soluble constituents of components (b) and (c) minus any solvent present.

The above alkaline builders defined under (b) need have no complex-forming ability at all. The usually inorganic salts frequently known as wash alkalis" are preferably used here. In particular cases, free bases, especially alkali metal hydroxide, may also be used. The alkaline builders according to (b) may have a certain amount of complex-forming ability. The above specifications for the component (b), however, only apply to those fractions whose complex-forming ability does not exceed the limits indicated above.

The presence of substances with higher complex-forming capacity is in no may excluded by this. On the contrary, the builders according to (b) are preferably present together with complex-forming compounds whose ability to form complexes lies above 230 mg. of CaCO per gram of complex-forming compound according to the Hampshire test. The ratio of alkaline builders to complex-forming compound may vary within wide limits. A synergistic action between antimicrobial substance and complex-forming compound (above 230 mg. of CaCO per gram) is already found when the amount of this complex-forming compound constitutes at least 3 percent and preferably at least percent by weight of the washing preparation. The fraction of complex-forming compound in the mixture of complex-forming compound and alkaline builders (b) may amount to 10 to 90 percent, preferably 25 to 75 percent by weight.

The same quantitative data supply here also under the same provisos, to the extent that they relate to the whole preparation and not to parts or partial mixtures thereof.

The alkaline builders within the meaning of the invention also include bleaching components, provided they themselves have an alkaline reaction, or the compounds remaining after the release of the active oxygen have an alkaline reaction. Some bleaching components, as for example monopersulfates or diacyl peroxides, and especially dibenzoyl peroxide, them selves have an acid reaction or provide acid reaction products after the evolution of the oxygen. These nonalkaline-reacting substances may be used as bleaching components in the products according to the invention provided sufficient alkali is present to maintain the pH at the desired value.

If the washing agent and washing adjuvant preparations according to the invention are intended for use with textiles, they should have pH values of about 8 to l2 in a 1 percent aqueous solution. These pH values are generally adjusted to the weaker alkaline values (pH 8 to 9.5) for fine washing agents and to the more strongly alkaline values (pH 9.5 to 12 preferably 10 to 11.5) for washing agents, for use at higher temperatures up to the boiling point. Also products often intended for cleaning the surfaces of solid materials, with the exception of textiles, in the house, in professional operations and in industry may have pH values of this kind. Still more strongly alkaline-reacting products may also be produced, which for example contain free caustic alkalis, and which, in general, are only used for special purposes.

The washing agents according to the invention can be used for the washing and washing with bleaching of a large variety of fibers of natural or synthetic origin, such as for example, cotton, regenerated cellulose or linen, as well as for the socalled easy care" textiles, which consist wholly or partly of highly finished cotton or of synthetic chemical fibers, such as for example, polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers. Also washing adjuvants, such as steeping or afterrinsing preparations, which contain the antimicrobial substances to be used according to the invention, can also be used with advantage. Hair and body washing agents, cleaning agents for the hands and cleaning agents for instruments or for industrial plants, as for example, dairies, breweries and so on, also belong to the preparations according to the invention.

The preparations according to the invention may be produced as lumps, tablets, powders, granulates, ag-

glomerates, pastes or solutions. Apart from preparations in which the pasty nature is due essentially to the presence of corresponding amounts of pastelike surface-active compounds (nonionics), the pasty or liquid nature of the preparation of the invention is mostly due to the presence of corresponding amounts of liquid solvents, in which the other components of the preparation are suspended or dissolved. The content of solvent in these preparations may amount to 40 to 90 percent, preferably 50 to percent by weight.

Water is the preferred solvent, but it may be wholly or partly replaced by water-soluble organic solvents. as, for example, monohydric alcohols with one to four, preferably two or three carbon atoms, polyhydric alcohols with two to five carbon atoms, partial ethers of these polyhydric alcohols with one another or with the said monohydric alcohols. Examples of these comprise alkanols such as ethyl, nor iso-propyl alcohols, alkanediols and triols such as ethylene glycol, glycerine; alkoxyalkanols such as ethylene glycol monomethyl or monoethyl ethers, glycerine monoor di-ethers of methyl or ethyl alcohols; and so forth.

In the preparations, according to the invention, water may be present as water of crystallization in salts, especially inorganic salts Na,c0,-10i-i,o, Na PO; l 2H O, N a P O '6H O). This water is not to be regarded as solvent.

The substituted phenyl ethers of the formula R4 O-R1 in which R, may be a lower aliphatic radical with one to four carbon atoms, which may be substituted by fluorine, chlorine, bromine, iodine or hydroxyl groups or be interrupted by an oxygen atom, and preferably-a member selected from the group consisting of alkyl having one to four carbon atoms, alkenyl having one to four carbon atoms, haloalkyl having one to four carbon atoms, hydroxyalkyl having one to four carbon atoms and alkoxyalkyl having one to four carbon atoms, and R R R R and R may be hydrogen, fluorine, chlorine, bromine, iodine, the trifluoromethyl radical or another aliphatic radical with one to four carbon atoms, a phenyl or nitro, and preferably members selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, halogen, trifluoromethyl, phenyl and nitro, are suitable as antimicrobial substances. The phenyl ethers substituted by halogenatoms or nitro groups are of course preferred. Par ticularly favorable results can be obtained in many cases with phenyl ethers substituted by halogen on the phenyl nucleus, the aliphatic ether component of which is substituted by a hydroxyl group or is interrupted by an oxygen atom, since with their aid preparations with specially high activity, that is with possibly specially low bactericidal or fungicidal concentrations with satisfactory activity can be prepared. Among these preferred compounds are phenyl ethers of the formula Rm n l l R where R is a member selected from the group consisting of hydrogen, methyl and ethyl, and R R R R and R are members selected from the group consisting of hydrogen, chlorine, bromine and alkyl having from one to four carbon atoms with the proviso that at least one of R R R R and R is chlorine or bromine.

Substituted phenyl ethers, which are suitable as bactericidal or fungicidal agents, are for example, 3-methyl-4-chlorophenylmethylether, 3,5-dimethyl-4-chloro-phenylmethylether, 2,4,-trichloro-phenylethylether, 3-( 3 ,5

dimethyl-4'-chloro-phenoxy)-propenel 3-( 2', 4',6'- trichlorophenoxy)-propene-l, 2 -phen0xy-e tl 1 ag- 1 -9 l 2;( 3 methyl-phenoxy)-ethan- 1 -ol, 2-( 2-methyl-phenoxy)-ethanl ol, 2-(4'-tert.-butyl-phenoxy)-ethan-1-ol, 2-(2',5-dimethylphenoxy)-ethan- 1 -ol, 2-( 3',5 -dimethyl-phenoxy)-ethan- 1 -ol, 2-( 2'-isopropyl-5'-methyl-phenoxy )-ethanl -ol, 2-( 2'-phenylphenoxy)-ethan-l-ol, 2-(2-chloro-phenoxy)-ethan-1-ol, 2-(4 -chloro-phenoxy)-ethan- 1 -ol, 2-( 2 ,4 '-dichloro-phenoxy ethan-l-ol, 2-(2,4',6-trichloro-phenoxy)-ethan-l-ol, 2-(4- iodo-phenoxy)-ethan-1-ol, 2-( 3 -methyl-4'-chloro-phenoxy ethan-l-ol, 2-(3,5'-dimethyl-4'-chloro-phenoxy)-ethan-l-ol, 2-(3-methyl- 4-bromo-phenoxy )-ethan-l-ol, 2-(4'-nitrophenoxy )-ethan- 1 -ol, l-methyl-2-( phenoxy )-ethan- 1 -ol, 1- ethyl-2-(phenoxy)-ethan-l-ol, l-methyl-2-(3',5-dimethylphenoxy )-ethan- 1 -ol, 1-methyl-2-( 2 -isopropyl-5 -methylphenoxy )-ethan- 1 -ol, 1-ethyl-2-( 3 ,5 '-dimethyl-phenoxyethan- 1 -ol, l-ethyl-2-( 2 -isopropyl-5 '-methyl-phenoxy ethan-l-ol, l-methyl-2-(2'-chloro-phenoxy)-ethan-l-ol, lmethyl-2-(4'-bromo-phenoxy)-ethan-1-ol, l -ethyl-2-( 2 chloro-phenoxy )-ethan- I -ol, l-ethyl-2-ethyl-( 4 'bromophenoxy )-ethanl-ol, l -methyl-2-(4'-iodo-phenoxy)-ethanl ol, l-ethyl-2-(4'-iodo-phenoxy-ethan-l-ol, l-methyl-2-(2'- methyl-4'-bromo-phenoxy )-ethanl -ol, l-ethyl-2-( 2 '-methyl- 4-bromo-phenoxy )-ethanl -ol, l-methyl-2-(4'-bromo-3,5 dimethyl-phenoxy)-ethan-1-ol, l-ethyl-2-(4'-bromo-3 ,5 dimethyl-phenoxy )-ethan- 1 -ol, l-methyl-2-( 4 '-bromo-5'- methyl-2 '-isopropyl-phenoxy )-ethan- 1 -ol, l-ethyl-2-( 4- bromo-5'-methyl-2'-isopropyl-phenoxy)-ethan-l-ol, 1-ethyl- 2-( 2 '-nitro-phenoxy )-ethan- 1 -ol, l-chloro-2-phenoxy-ethane, l-chloro-2-( 2 -methyl-phenoxy)-ethane, l-chloro-2-( 3 methyl-phenoxy-ethane, l-chloro-2-(2-phenyl-phenoxy ethane, l-chloro-2-(2'-chloro-phenoxy)-ethane, l-chloro-2- (3 '-methyl-4'-chloro-phenoxy )-ethane, (3-methyl-phenoxy)- methyl-ethyl-ether and (4-chloro-phenoxy)-methyl-ethylether.

Examples of fluorine-containing antimicrobial substances include 2-(4'-fluoro-phenoxy)-ethan- 1 -ol, 2-( 2'-fluorophenoxy )-ethanl -ol, l-methyl-2-(4'-fluoro-phenoxy)-ethanl-ol, l-ethyl-2-( 4 '-fluoro-phenoxy )-ethan- 1 -ol, 2-( 4'- trifluoromethyl-phenoxy )-ethan- 1 -ol.

Surface-active compounds, possibly including textile softeners, foam stabilizers and/or foam inhibitors, dirt carriers, enzymes, bleaching components and stabilizers for the bleaching components, belong to the other constituents customary in washing agents, washing adjuvants and cleaning agents according to the definition of the invention, and, if percompounds are concerned, also activators for these, scouring agents, perfumes, dyestuffs, and so forth.

The composition of the washing agents, washing adjuvants and cleaning agents according'to the invention, apart from the antimicrobial substance which is present in amounts from 1 to 30 percent preferably 2 to 5 percent by weight, lies in general within the range of the following formulation:

to 90 percent, preferably to 40 percent and especially 12 to 30 percent by weight of surface-active compounds, possibly including textile softeners or combinations of surface-active compounds, consisting of:

0 to 100 percent, preferably 25 to 65 percent by weight of surface-active compounds of the sulfonate and/or sulfate type with preferably eight to 18 carbon atoms in the hydrophobic residue,

0 to 100 percent, preferably 5 to 40 percent by weight of nonionic surface-active compounds,

0 to 100 percent, preferably to 50 percent by weight of soap,

0 to 6 percent, preferably 0.5 to 3 percent by weight offoam stabilizers,

0 to 8 percent, preferably 0.5 to 5 percent by weight of nonsurface-active foam inhibitors,

5 to 99 percent, preferably 10 to 70 percent by weight of the usual alkaline-reacting builders according to the above definition, which may be present in combination with complexforming compounds according to the above, definition, where the complex-forming compound preferably constitutes at least 3 percent especially at least [0 percent by weight of the total preparation,

0 to 50 percent, preferably 2 to 15 percent by weight of other washing agent constituents such as,

for example, dirt carriers, optical brighteners, enzymes, perfumes, dyestuffs, water.

When the preparations according to the invention have been prepared by spray drying, they usually contain not more than 25 percent by weight and preferably not more than 20 percent by weight of water. If, however, the preparations have been converted into a solid state from an aqueous, pastelike starting composition by tying up the liquid water, then the water content may amount to up to 50 percent.

The washing agents and washing adjuvants according to the invention may further contain bleaching components, which, including activators and/or stabilizers for the percompound present, then constitute 10 to 50 percent, preferably l5 to 35 percent by weight of the total washing agent. The bleaching component is generally present in an amount such that its content, calculated as active oxygen, amounts to 1 to 4 percent, preferably 1.5 to 3.5 percent by weight. Provided these bleaching agents or the substances formed therefrom after the release of the active oxygen have an alkaline reaction, they are to be regarded as alkaline builders for purposes of calculation of the ingredients of the preparations of the invention.

In the washing agent, the total amount of alkaline-reacting builders and complex-forming compound possibly present is preferably 0.5 to 7 times, and especially 1 to 5 times the total amount of the combined surface-active components present.

The cleaning agents according to the invention may also contain mechanical cleaning substances, the latter usually being present in amounts of at least 30 percent by weight, preferably 50 to 98 percent and especially 75 to percent by weight. Suitable mechanical cleaning substances are preferably fine powders of mostly water-insoluble substances, as for example, quartz flour, marble dust, ground pumice and so forth. The remainder (not more than 70 percent, preferably 50 to 2 percent and especially 25 to 5 percent by weight) consists to the greater part of water-soluble components of the composition according to the invention. Owing to this, the concentration of the antimicrobial compounds referred to the total product may be relatively small. However, since these products, especially the much used scouring agents, are moistened during their use with only a little water, an entirely adequate concentration of active substances is obtained in spite of the small content of active substances.

The possibly present anionic, amphoteric or nonionic surface-active compounds in the products according to the invention contain in the molecule at least one hydrophobic residue of 8 to 26, preferably l0 to 20 and especially 12 to 18 carbon atoms and an anionic, nonionic or amphoteric water-solubilizing group. The preferably saturated hydrophobic residue is usually aliphatic or alicyclic, and it may be connected directly with the water-solubilizing groups or via intermediate members. Suitable intermediate members are benzene rings, carboxylic acid ester or carbonamide groups, residues of polyhydric alcohols linked in ether or ester form, as for example those of ethylene glycol, propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residue with 10 to 18 carbon atoms, but deviations from this preferred range of carbons are possible, depending on the nature of the respective surface-active compound.

Soaps derived from natural or synthetic fatty acids, possibly also from resin or naphthenic acids, are utilizable as anionic detergents. Fatty, resin or naphthenic acids of natural origin are often more or less unsaturated. They are preferably used in a partly or completely hydrogenated state, so that they have iodine values of not more than 30 and preferably of less than 10.

Of the synthetic anionic surface-active compounds the sulfonates and sulfates have special practical importance.

Examples of the sulfonates are the alkylarylsulfonates, especially the alkylbenzenesulfonates, which are obtained from preferably straight-chain aliphatic hydrocarbons with nine to 15, preferably to 14 carbon atoms, by chlorinating and alkylating benzenes or from corresponding olefins with terminal or nonterrninal double bonds by alkylating of benzene, and sulfonating the alkylbenzenes obtained. Furthermore, aliphatic sulfonates are of interest such as are obtainable from preferably saturated hydrocarbons containing eight to 18 and preferably 12 to 18 carbon atoms in the molecule by sulfochlorinating with sulfur dioxide and chlorine or sulfoxidating with sulfur dioxide and oxygen and conversion of the products thereby obtained into the sulfonates. Further, mixtures of alkene-sulfonates, hydroxyalkene-sulfonates and hydroxyalkane-sulfonates are useful as the aliphatic sulfonates, which are obtained, for example, from terminal or nonterminal, C -C and preferably C -C olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products. In the aliphatic sulfonates thus prepared, the sulfonate group is frequently attached to a secondary carbon atom. Sulfonates with a terminal sulfonate group can also be prepared, however, by reacting terminal olefins with bisulfite.

The sulfonates to be used according to the invention also include salts, preferably di-alkali metal salts of asulfo-fatty acids, and also salts of esters of these acids with monoor poly-hydric alcohols containing one to four and preferably one to two carbon atoms.

Further useful sulfonates are the fatty acid esters of oxyethanesulfonic acid and dihydroxypropanesulfonic acid, the fatty alcohol esters of lower aliphatic or aromatic sulfomonoand di-carboxylic acids containing one to eight carbons atoms, the alkylglycerylether-sulfonates and the condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Surface-active compounds of the sulfate type include fatty alcohol sulfates, especially those from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol. Useful sulfonation products of the sulfate type can also be made from terminal or nonterminal C C olefins. Further, belonging to this group of surface-active compounds are sulfated fatty acid alkylolamides, sulfated monoglycerides and sulfation products of ethoxylated and/or propoxylated fatty alcohols, alkylphenols with eight to carbon atoms in the alkyl residue, fatty acid amides, fatty acid alkylolamides and so forth, in which case 0.5 to 20, preferably one to eight, and advantageously 2 to 4 mols of ethylene oxide and/or propylene oxide may be added to 1 mol of the said compounds to be ethoxylated and/or propoxylated.

The washing agents according to the invention may also contain surface'active synthetic carboxylates, for example, the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the condensation products of fatty acid or sulfonic acids with aminocarboxylic acids, for example with glycocoll, sarcosine or protein hydrolysates.

The nonionic surface-active compounds, here for simplicity called Nonionics," include products which owe their solubility in water to the presence of polyether chains, amineoxide, sulfoxide or phosphineoxide groups, alkylolamide groups and very generally to an accumulation of hydroxyl groups.

The products obtainable by the addition of ethylene oxide and/or glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid and sulfonic acid amides, are of particular practical interest, and these nonionics may contain 4 to 100, preferably 6 to 40, and especially 8 to ether oxygens, particularly ethylene glycol ether oxygens, per molecule. Moreover, propylene or butylcne glycol ether oxygens may be present in and/or at the end of these polyglycol ethers.

Further, the nonionics include the water-insoluble polypropylene glycols which have been made water-soluble by addition of ethylene oxide and are known by the trade names of"Pluronics, Tetronics" and Ucon Fluid, and also addition products of propylene oxide to alkylenediamines or lower aliphatic alcohols containing one to eight and preferably three to six carbon atoms.

Further useful nonionics are fatty acid or sulfonic acid alkylolamides, which are derived, for example, from monoor di-alkylolamines, dihydroxypropylamine or other polyhydroxyalkylamines, for example the glycamines. They can be replaced by amides of higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

From the group of amine oxides, the nonionics derived from higher tertiary amines having a hydrophobic alkyl residue and two shorter alkyl and/or alkylol residues each containing up to four atoms are of special interest.

Amphoteric or zwitterion surface-active compounds contain at least one acid and at least one basic hydrophilic group in the molecule. The acid groups include carboxyl, sulfonic acid, sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups. Suitable basic groups are primary, secondary, tertiary and quaternary ammonium groups.

Carboxy-, sulfateand sulfonate-betaines, owing to their good compatibility with other surface-active compounds, have special interest in practice. Suitable sulfobetaines are obtained, for example, by reacting tertiary amines containing at least one hydrophobic alkyl residue with sultones, for example propaneor butanesultone. Corresponding carboxybetaines are obtained by reacting the said tertiary amines with chloracetic acid, its salts or chloracetic acid esters, and splitting of the ester linkage.

The foaming power of the surface-active compounds used can be increased or reduced by a combination of suitable surface-active compounds, and the foaming power can of course also be changed by additions of compounds other than surface-active compounds.

The above mentioned nonionics of the alkylolamide type are known to be suitable as foam stabilizers. Fatty alcohols or higher alkane terminal diols are also utilizable for this purpose.

The foaming power of synthetic anionic or nonionic surface-active compounds can be reduced by addition of soaps, and with certain combinations of synthetic anionic surface-active compounds, nonionics and soap, the foaming power is still more greatly reduced. Further, the products of addition of propylene oxide to the above-described surface-active polyethylene glycol ethers are marked by a small foaming capacity, while by varying the number of ethylene glycol and propylene glycol residues present in the molecule, products with a wide variety of turbidity points can be made. These nonionics act as foam inhibitors on other nonionics at temperatures above their turbidity point. They can also be combined with other surface-active compounds or mixtures of different surface-active compounds.

Mixtures of anionic surface-active compounds, especially those of the sulfonate and/or sulfate type, nonionic surface-active compounds and soaps have attained great practical importance, and the foaming tendencies of such combinations may be varied by the choice of the soap. If, for example, these soaps contain 12 to 18 carbon atoms in the fatty acid residue, the mixtures of surface-active compounds show a certain inhibition of foaming, which however is often not sufficient when the washing agents are to be used in drum washing machines at temperatures from 60 to C. In such cases a powerful repression of foaming of synthetic anionic, amphoten'c and nonionic surface-active compounds is obtained by soaps of fatty acid mixtures with 20 to 30, preferably 20 to 26 carbon atoms.

The surface-active compounds, however, may also be combined with known foam inhibitors which are not surface-active. These include N-alkylated aminotriazines, possibly containing chlorine, which are obtained by reacting 1 mol of cyanuric chloride with 2 to 3 mols of a monoand/or di-alkylamine with six to 20, preferably eight to 18 carbon atoms in the alkyl residue. Paraffins, halogenated paraffins and aliphatic C to C ketones, can also be used as foam inhibitors, especially in combination with soaps.

By choice of suitable foam inhibitors, it can be arranged that the foam-repressing action does not start until a specified temperature has been exceeded, so that washing agents can be made which still foam in the middle range of temperature up to, for example, 65 C., but which produce less and less foam as the temperature is increased beyond this point. Foam stabil' izers and foam inhibitors dependent on temperature can even be combined together.

Foam inhibitors dependent upon temperature include the above-mentioned N-alkylated aminotriazines, and paraffins, halogenated paraffins, ketones etc., the foam-repressing action of which becomes particularly strong at temperatures above their melting point. The higher soaps derived from fatty acids with 20 to 30 carbon atoms in the molecule also show a similar action. These soaps may be added in varying amounts, and may constitute to 100 percent of the total soap fraction present in the surface-active component.

To the above-defined alkaline-reacting builders belong, preferably, the usual, alkaline-reacting constituents of washing and cleaning agents and washing adjuvants, as well as the complex-forming compounds acting synergistically with the antimicrobial substances. The components according to the invention may also contain neutral-reacting salts in addition to these constituents. Such salts are enumerated below essentially according to their chemical nature, without anything being said as to whether they belong to the weaker or stronger complex-forming compounds defined above or to the alkaline builders.

According to the invention, useful, neutral weakly or more strongly alkaline-reacting salts are, for example, the bicarbonates, carbonates or silicates of the alkali metals, mono-, dior tri-alkali metal orthophosphates, dior tetra-alkali metal pyrophosphates, alkali metal metaphosphates known as complex-forming compounds, alkali metal sulfates, and the alkali metal salts of organic, nonsurface-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing one to eight carbon atoms. These include, for example, water-soluble salts of benzene-, tolueneor xylenesulfonic acids, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or the salts of sulfodicarboxylic acids, and also the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Higher molecular weight polycarboxylic acids or their water-soluble salts may also be present, especially salts of polymerizates of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylene-malonic acid and citraconic acid. Salts of copolymerizates of these acids with one another or with other polymerizable substances, as for example, with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3-methyl-3-butenecarboxylic acid and also with vinylmethylether, vinyl acetate, isobutylene, acrylamide and styrene are also useful.

Belonging to the organic complex-forming compounds are, for example, nitrilotriacetic acid, ethylenediuminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complex-forming compounds. Combinations of different complex-forming compounds can also be used. Other known complex-fonning compounds also include diand polyphosphonic acids of the following constitution:

in which R represents alkyl and R represents alkylene, both with one to eight, preferably one to four carbon atoms, and X and Y represent hydrogen atoms or alkyl with one to four carbon atoms. Carboxy-methylenephosphonic acid, (HOOC- CH PO(OH) is also utilizable as a complex-forming compound according to the invention. All these complex-forming compounds may be present as the free acids, but it is preferred to use them as the alkali metal salts.

The following table 1 contains data on the ability to form complexes of various compounds determined by the Hampshire test. The operation of the Hampshire test is described in the examples.

TABLE I Calcium carbonate binding Complex forming compound capacity 1 Hydroxymethylphosphonic acid 1 Mesoxalic acid monohydrate 6 l-cysteine hydrochloride monohydrate- 14 Glycollic acid 45 Tetrasodium pyrophosphate n-Hexylaminodimethylenephosphonic acid. Sodium tripolyphosphate 214 Hexamethylenediaminetetramethylenephosphonic acid 220 l-hydroxyhexane-l,l-dipho=phonic acid 280 a-Aminoethane-a,a-diphosphonic acid 930 a-Aminobenzyl-a,adiphosphonic acid 1, 460 Aminotrimethylenephosphonic acid 20 Ethylenediaminetetramethylenephosphonic acid. 860 Aminodimethylenephosphonic acid-N-acetic acid. 860 Iminodiacetic acid-N-methylenephosphonic acid. 540 Hydroxyethanediphosphonic acid 810 Phosphonoacetic acid 270 Citric acid 323 Diethylenetriaminepentaacetic 275 1,Z-cyclohexanediaminetetraacetic a 285 Ethylenediaminetetraacetic acid 402 N itrilotriacetic acid 678 C O O H C O O H 250 Technical mixture of various metaphosphates (Grahams salt) 1 In mgJg. of complex-forming compound.

tion NaBO -H O may also be used in its place. Finally,

borates containing active oxygen, NaBO 'l-l O are also useful in which the ratio Na,o:B,o, is less than 0.5 to l and lies preferably in the range from 0.4-0.15 to l, and in which the ratio H O :Na lies in the range of 0.5-4 to 1. These products are described in the German Pat. No. 901,287 and in the U.S. Pat. No. 2,491,789.

The perborate may be wholly or partly replaced by other inorganic percompounds, especially by peroxyhydrates, as for example, the peroxyhydrates of ortho-, pyroor polyphosphates and carbonates.

The washing and cleaning agents and washing adjuvants according to the invention may contain up to percent preferably from 0.5 to 8 percent by weight of the usual waterinsoluble or water-soluble stabilizers for percompounds.

Suitable water-insoluble percompound stabilizers are the various magnesium silicates. Precipitation products which are formed on bringing together aqueous solutions of alkali metal silicates with solutions of magnesium salts are mostly concerned here. The proportion MgOzSiO, may lie in the range of from 4:1 to 1:4, preferably from 2:1 to 1:2. A product with a proportion of MgOaSiO, of 1:1 is frequently used. These magnesium silicates may be replaced by the corresponding silicates of other alkaline earth metals, cadmium or tin. Watercontaining tin oxides are also useful as stabilizers. These stabilizers are usually present in amounts from 1 to 8 percent, preferably 2 to 7 percent of the weight of the total preparatron.

The water-insoluble percompound stabilizers may be wholly or partly replaced by water-soluble substances. As such are suitable, above all, the above-enumerated substances with a complex-forming capacity above 230 mg. of CaCO per gram. Provided these are only to stabilize the active oxygen and/or the brightener, without a simultaneous synergistic action with the antimicrobial substances being produced, they may be present in amounts from 0.1 to 5 percent preferably from 0.2 to 2.5 percent of the weight of the total preparation, depending on the stabilizing ability of the complex-forming compounds.

The active chlorine compounds utilizable according to the invention may be inorganic or organic.

The inorganic active chlorine compounds include alkali metal hypochlorites, which can be used especially in the form of their mixed salts or addition compounds with orthophosphates or condensed phosphates such as, for example, pyroand polyphosphates or with alkali metal silicates. 1f the washing agents and adjuvants contain monopersulfates and chlorides, active chlorine is formed in aqueous solution.

Specially suitable organic active chlorine compounds are the N-chloro compounds, in which one or two chlorine atoms are linked to a nitrogen atom, the third valency of the nitrogen atom preferably being satisfied with a negative group, especially a CO or SO group. These compounds include dichloroand trichloro-cyanuric acid, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.

The preparations according to the invention may also contain enzymes. These, in combination with the disinfectants, have the advantage of loosening protein-, starchor fat-containing contaminations and exposing the microbes possibly en closed therein and bringing them in contact with the antimicrobial substances. The enzymes may be of a variety of types, and may be proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, liases, transferases, desmolases or nucleases. Proteases, amylases and lipases are of particular practical interest, and above all the active enzymatic substances obtained from Bacillus subtilis and streplornyces griseus, especially those of proteolytic nature. Further useful enzymes are pepsin, pancreatin, trypsin, papain and diastase.

' The antimicrobial substances to be used according to the invention have the special advantage of being inert towards optical brighteners, which may be contained chiefly in washing agents and adjuvants.

Examples of optical brighteners from the class of diaminostilbenesulfonic acid derivatives are compounds of the following formula:

In this formula R signifies a hydrogen atom, an alkyl or aryl residue, which may possibly be substituted, Ar and Ar signify aryl residues such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms.

Soil suspension agents may also be contained in the preparations of the invention, which keep the dirt, detached from the fibers, suspended in the liquor, and thus prevent greying. Water-soluble colloids of mostly organic nature are suitable for this purpose, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ethercarboxylic acids or ethersulfonic acids of starch or of cellulose, or salts of acid sulfuric acid esters of cellulose or of starch. Water-soluble polyamides containing acid groups are also suitable for this purpose. Further, starch and other than the above-mentioned starch products can be used, such as degraded starch,.aldehyde starches and so on. Polyvinylpyrrolidone is also useful.

EXAMPLES The following examples describe the compositions of some preparations according to the invention. They are not to be deemed to be limitative in any respect however.

The saltlike components contained therein, such as saltlike surface-active compounds, other organic salts as well as inorganic salts are present as the sodium salts, unless otherwise stated. The names or abbreviations utilized are defined as follows:

ABS" is the alkali metal salt of an alkylbenzenesulfonic acid with 10 to 15, preferably ll to 13 carbon atoms in the alkyl chain, obtained by condensing straight-chain olefins with benzene and sulfonating the alkylbenzene thus formed.

Alkanesulfonate is an alkali metal sulfonate obtained from paraffins with 12 to 16 carbon atoms by sulfoxidation.

Fs-estersulfonate" is an alkali metal sulfonate obtained from the methyl ester of a hardened tallow fatty acid by sul fonating with S0 Olefinsulfonate is an alkali metal sulfonate obtained from mixtures of olefins with 12 to 18 carbon atoms on sulfonating with $0 and hydrolyzing the sulfonation product with caustic solution, the sulfonate consists substantially of alkene sulfonate and hydroxyalkane sulfonate, but also contains, in addition, small amounts of alkane disulfonates. Each olefin sulcorporated in the same way as described with the foam inhibifonate-containing preparation was prepared using two different types of olefin sulfonates; one was prepared from a mixture of straight-chain terminal olefins, and the other was prepared from a mixture of olefins with a nonalpha double bond.

KA-sulfonate and TA-sulfonate are the alkali metal salts of sulfated substantially saturated fatty alcohols, prepared by reduction of coconut fatty acid (KA) and tallow fatty acid (TA) respectively.

KA-EO-sulfonate and TA-EO-sulfonate" and OA-EO- 10 sulfonate are the sulfated products of addition of 2 mols of ethylene oxide to 1 mol of coconut fatty alcohol (KA), 3 mols of ethylene oxide to 1 mol of tallow fatty alcohol (TA), and 2 mols of ethylene oxide to 1 mol of oleyl alcohol (A) respectively.

OA-i-SEO, OA+l0EO" and KA-i-ZOEO are the products of addition of ethylene oxide (E0) to technical oleyl alcohol (OA) and coconut alcohol (KA), while the numbers represent the molar amount of ethylene oxide added to 1 mol of alcohol.

KA+9EO+12PO" is a nonionic surface-active agent obtained by reacting 1 mol of "KA+9EO with 12 mols of propylene oxide.

Perborate" is a product of the approximate composition NaBO -H O -BH O, containing about 10 percent of active Oxygen NTA," "EDTA" and "EHDP" are the alkali metal salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid and hydroxyethanediphosphonic acid respectively.

CMC is the alkali metal salt of carboxymethylcellulose.

BW-Brightener I" and BW-Brightener ll" are the commercial products Purwil 4" and Blankophor BBH/Sll" respectively, preferably specified for use with cotton.-

PA-Brightener" is the commercial product Purwil P," preferably specified for use with polyamides.

PE-Brightener l" and "PE-Brightener II" are the commercial products Uvitex SOF and Calcofluor white ALF" respectively, preferably specified for use with polyester.

The composition of the fatty act mixtures, from which the various soaps contained in the products according to the invention were prepared. may be taken from the following table ll:

TABLE IL-COMPOSITIONDF THE FATTY ACID MIXTURES CORRESPONDING TO THE SOAPS Percent by Weight of fatty acid componant in- Number of carbon atoms in the Soap Soap Soap Soap fatty acid 101s 1222 .1222 u 1622 W s 17 32 so 32 4 a 12 21 4 48 Iodine value of the fatty acid mixture 7. 5 8 76 4 A mixture of about 45 percent of a di-(alkylamino)- kylmelamine was used as foam inhibitor. ln all these triazinc derivatives, the alkyl residues are present as a mixture of homologs with eight to l8 carbon atoms. The monochlorotriazine derivative or the trialkylmelamine can also be used alone with a similar result. Provided the described products contain synthetic sulfates or sulfonates together with soap, the other nonsurface-active foam inhibitors mentioned in the description can also be used, as for example, paraffin oil or paraffin. In the production of the preparations, the foam inhibitor used was dissolved in a suitable organic solvent or sprayed in the molten state on the moving pulverulent preparation by means of a jet nozzle.

If the preparations according to the invention were present as pulverulent products, the antimicrobial substances were intors. Foam inhibitors and antimicrobial substances were of course sprayed on successively.

The composition of the preparations according to examples l to l2 can be seen from the following tables Ill and W. The sign in the line Na SO means that small amounts of sodium sulfate were present as impurities in the anionic surface-active compounds. The Roman numerals in the line antimicrobial substance" represent the substance present in each case, and in the line below, the amount of the substance is given. In the last line no values are given under Remainder; these can be calculated as the difference between 100 and the amounts of the other components. Of the preparations described, the residue consists to a substantial part of water. lf Na,SO is present only in small quantities arising from the synthetic anionic surface-active compound (sign in the Na SO, line of the table) the residue also contains the Na SO present. Moreover, any dyestuffs, perfumes and enzymes present come under the residue.

The following antimicrobial substances were used:

The products described in the examples l to 12 can be preferably used for the following purposes:

Example 1: Sleeping agent or complete washing agent.

Examples 2-4 and 6-9: All purpose washing agent.

Example 5: Washing agent for colored goods free from perborate and brighteners.

Example l0: Washing agent for colored goods free from brighteners. but containing per orate.

Examples 1 I Fine washing agent: also and I2: intended for use with easy-cure textiles.

All washing agents described above may be used in drum washing machines even at temperatures of from to I00" C. without foaming over.

TABLE III Percent by Weight of component in the preparation according to Example No.-

Components of the preparation 1 2 3 4 5 ABS 0.0 11.0 Olefin sulfonate 5. 0 .5 Soup 1018 l 0 Soap 1622. .2 0 OA-HS E0. b I] 0A+10 E0 x n u." KA+20 E0- 1'3. 0 KA+9 EO.. 3.0 7.5 KA+12 Po-.- Foam inhibitor 0 3 0 5 0. 8

1. Antimicrobial substance IOM OIN HUI Quantity BW-Brightener BW-Brightcner II. PA-B rightener. lE-Brightener I. PE-Brightener II Residue ll cel lllsia Sm lllll TABLE IV Percent by weight of component in the preparation according to Example No.-

Components of the preparation 6 7 8 9 10 57% 59% by weight ofa l-alkancsulfonate,

prepared from mixture ol'olcfins with terminal double bonds containing l2-l8 carbon atoms. by addition of sodium bisullitc. 20% 29% by weight of soap (80 of tlllow and 20of coconut fatty acid) 5% 5% by weight of antimicrobial substance ll 3% by weight of NTA. EDTA or EHDP 7% 7% by weight of water EXAMPLE l6 A bottle-washing agent used in the liquor industry had the following composition:

53.0% by weight of commercial sodium hydroxide. ABS 8. 15.0% by weight of tetrapolyphosphute Alkane sulionate. 7. 5 10.0% by wei ht or Nu,O-3-3Si0, g?$g fi g$: 8'6 12.0% by weight of aminotri-( mcthylenephosphate) Kgfsulfafih L 6 2' B L 7 1 5 2 l0.0% by weight of antimicrobial substance Vll 1Xsfi1gateif 0.5 3. 0 2; 1. 5 7- -su ate 2.0 .5 TA-EO-sulfate. 7. 5 EXAMPLE 1? 0A-E(())isulfate 5. 5 4 Soap 1 8 15 Soap 1222 5' 8 u 3 m 2 a 5 A wasl nng agent for prewashlng which even at temperatures Soap 1222 u 6.8 up to 60 C. makes possible an extensive, if not complete (.115- gii I I I infection, had the following composition: Foam inhibitor 0. 6 0. 8 0. 9 8.0% by weight of ABS. ulkunesulfonatc or olefinsulfonute 4i i 4:; g 10L? 40% by weight of Soup I622 24. 0 38. 0 21. O 33. 0 35. O 48. 0 0.3% by weight of foam inhibitor 25. 0 23. 6 2g. 1 22-3 I 36.0% by weight of Na,P,O 5. 0 0 10. O 7.5% by weight of NaOH 0. 25 0. 5 0. 4 08% y Welsh! Of 1 M 1. 3 1. 9 1. 2 1. 4 1. 5 1. 3 1. 7 24.0% by weight of antimicrobial substance Antimicrobial substance VIII III IX V II VII VI VII Quantity 4. 7 3. 9 6. 4 3. 75 9. 1 2. 6 5. 4 J I r W'cl fi lgkv-grightener n o. 5 o. 4 0. 2 o. 35

rightener 0. 04 0. 5 0. 03 PE-Brightener I 0.15 EXAMPLE l8 PE-Brightener II 0. 10 0. 7 Residue a An after-rinsing agent for laundered articles, which at the same time dissolves deposits on the fiber, especially lime-con- 4 taining deposits, had the following composition:

EXAMPLE 3 30.0% by weight of perborate 30.0% by weight of EHDP A liquid washing agent present as a pourable suspension of 16% y Weishwf antimicrobiul submit undissolved components in an aqueous solution had the foli I lowin composition" 80% by was! g 24.9% by weight of Na,SO,

10.0; by weight ABS 8.5% by weight coconut fatty acid dicthanolamide 6.0% by weight potassium toluenesulfonate EXAMPLE 20.0% by weight Na,P,O 0.0,; by weight Kano. antimicrobial fine washing agent had the following com |.s by weight CMC p sition:

81% by weight antimicrobial substance Vll Remainder water The antimicrobial action of this product is improved when the content of Na .,P;,O is reduced to 18 to 15 percent by weight and 2 to 5 percent by weight of EDTA or EHDP is incorporated therefor.

EXAMPLE 14 EXAMPLE 15 As described in example 14, two washing agent preparations were prepared of the following compositions a and b:

20.0% by weight of ABS l.5% by weight of toluenesulfonatc 5.0% by weight of KA-sulfate 25.0% by weight of sodium sulfate 1.0% by weight ofCMC 5.0% by weight of antimicrobial substance 30.0% by weight of NTA (disodium salt) Remainder water The above formulation can be varied by reducing the sodium sulfate to 10 percent by weight and adding 15 percent by weight of sodium tripolyphosphate or sodium pyrophosphate instead.

When articles to be washed are treated in the usual way using the preparations according to examples I to 13, and 17 to 19, an antimicrobial action is obtained which is prolonged over the whole time of treatment. If the products contain bleaching components, the antimicrobial action of the active substances used according to the invention is also still present before employment or after conclusion of the action of the bleaching component. lf after-rinsing agents with a content of H such antimicrobial substances are used in the last rinsing bath, the small quantities of antimicrobial substance remaining on the fiber also act after the end of the washing process and after the bleaching of the washed textiles.

5 EXAMPLE 20 A scouring agent with a disinfectant action had the following composition:

95% by weight of quartz flour. finely ground by weight ofa fine powder ofthe following composition: 20% by weight of ABS 35% by weight of Na P o um by weight of NTA l5 IS'K by weight of Na SO by weight of antimicrobial substance Vll Remainder water EXAMPLE 21 A disinfectant hand washing preparation had the following composition:

44.0% by weight of sodium lauryl sulfate 3.0% by weight of coconut fatty acid monoethanolamide 40.0% by weight of finely ground pumice 3.0% by weight of antimicrobial substance ll l0.0% by weight of NTA (disodium salt) EXAMPLE 22 An antimicrobial scouring agent had the following composition:

20.0% by weight of A85 (30. percent active substance) 2.0% by weight of sodium sulfate 10.0% by weight of NTA distidium salt) 30% by weight of antimicrobial substance Ill 5.0% by weight of finely ground pumice 60.0% by weight of finely ground quartz flour EXAMPLE 23 An antiseptic shampoo prepared as a clear aqueous solution had the following composition:

40.0% by weight of sodium lauryl ether sulfate (27-28% active substance) 6.0% by weight of coconut fatty acid diethanolamide 2.0% by weight of antimicrobial substance IV 2.0% by weight of EDTA Remainder water 5 5 EXAMPLE 24 A bubble bath preparation with an antimicrobial activity had the following composition:

65.0% by weight of sodium lauryl ether sulfate (27-28% active substance) 5.0% by weight of coconut fatty acid diethanolamide 3.0% by weight of antimicrobial substance V 2.0 by weight Ur EDTA Remainder water The advantage attainable with the preparations according to the invention consists in that it is possible to lower considerably the concentration of disinfecting components in the antimicrobial washing preparations without the germ-killing action thereof being reduced. This is of special importance in all the cases in which harmful or unpleasant side effects are caused by higher concentrations of the disinfectant components, such as may occur, for example, with body washing agents.

An exact description of the method of analysis for the determination of the calcium carbonate binding capacity is found in the publication of the Hampshire Chemical Corp. of June 1960 Hampshire NTA Technical Bulletin, Appendix S.A2. According to this, exactly 2 g. of pulverulent complex-forming compound are dissolved in 50 ml. of distilled water. The solution is neutralized, treated with l0 ml. of a 2 percent sodium carbonate solution, its pH value adjusted to l l to 12 and the solution diluted to I00 ml. It is then titrated with a calcium acetate solution, which contains 44.] g. of calcium acetate monohydrate per liter, until a distinct and lasting turbidity occurs. The calcium carbonate binding capacity of the complexforming compound is calculated by the formula:

Ml. calcium acetate solution 25 Weight of complex-forming compound =Mg. of CaCO bound per gram of OOIllPlCX-fOIIllillg v compound.

wherein R is a member selected from the group consisting of hydrogen, methyl and ethyl, and R R, R,,, R and R are members selected from the group consisting of hydrogen, chlorine, bromine and alkyl having from one to four carbon atoms with the proviso that at least one of R R R R and R is chlorine or bromine, (b) at least 5 percent by weight of alkaline-reacting builders which, in the Hampshire test, have a complex-forming ability of from 0 to not more than 230 mg. of CaCO per gram, selected from the group consisting of alkali metal hydroxides, bicarbonates, carbonates, silicates, orthophosphates, pyrophosphates, tripolyphosphates and sulfates, and (c) the remainder to parts by weight of complex-forming compounds which, in the Hampshire test, have a complex-forming ability of over 230 mg. of CaCO per gram, selected from the group consisting of grahams salt, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N- hydroxyethyl-ethylenediaminetriacetic acid, polyalkylenepolyamine-N-polycarboxylic acids, diphosphonic acids, polyphosphonic acids and carboxymethylenephosphonic acid.

2. The antimicrobial washing and washing adjuvant preparations of claim 11 wherein said antimicrobial component (a) is present in an amount of from 2 to 5 percent by weight.

3. The antimicrobial washing and washing adjuvant preparations of claim 2 wherein said component (b) is present in an amount ofat least 10 percent by weight.

4. The antimicrobial washing and washing adjuvant preparations of claim 1 containing at least 3 percent by weight of said complex-forming compounds of component (c) which, in the Hampshire test, have a complex-forming ability of over 230 mg. of CaCO per gram of said complex-forming compounds.

5. The antimicrobial washing and washing adjuvants preparations of claim 4 wherein said complex-fonning compounds are present in an amount of at least 10 percent by weight. 

2. The antimicrobial washing and washing adjuvant preparations of claim 11 wherein said antimicrobial component (a) is present in an amount of from 2 to 5 percent by weight.
 3. The antimicrobial washing and washing adjuvant preparations of claim 2 wherein said component (b) is present in an amount of at least 10 percent by weight.
 4. The antimicrobial washing and washing adjuvant preparations of claim 1 containing at least 3 percent by weight of said complex-forming compounds of component (c) which, in the Hampshire test, have a complex-forming ability of over 230 mg. of CaCO3 per gram of said complex-forming compounds.
 5. The antimicrobial washing and washing adjuvant preparations of claim 4 wherein said complex-forming compounds are present in an amount of at least 10 percent by weight.
 6. The antimicrobial washing and washing adjuvant preparations of claim 4 wherein said complex-forming compounds are present in an amount of between 10 to 90 percent of the amount of the mixture of said complex-forming compounds and said components (b).
 7. The antimicrobial washing and washing adjuvant preparations of claim 6 wherein said complex-forming compounds are present in an amount of between 25 to 75 percent of the amount of the mixture of said complex-forming compounds and said components (b).
 8. Antimicrobial washing and washing adjuvant preparations consisting essentially of (a) from 1 to 30 percent by weight of a substituted phenyl ether antimicrobial component of the formula
 9. The antimicrobial washing and washing adjuvant preparations of claim 8 having a further content of from 10 to 50 percent by weight of neutral to alkaline-reacting perborate bleaching compounds and water-insoluble magnesium silicate stabilizers.
 10. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said component (b) comprise from 75 to 90 percent by weight.
 11. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 2-(4''-chlorophenoxy)-ethan-1-ol.
 12. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 2-(2'' ,4'' -dichlorophenoxy)-ethan-1-ol.
 13. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 2-(2'' ,4'' ,6''-trichlorophenoxy)-ethan-1-ol.
 14. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 2-(3''-methyl-4''-chlorophenoxy)-ethan-1-ol.
 15. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 2-(3''-methyl-4''-bromophenoxy)-ethan-1-ol.
 16. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 1-methyl-2-(2''-isopropyl-4''-bromo-5''-methylphenoxy)-ethan-1-ol.
 17. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 1-methyl-2-(2''-methyl-4''-bromophenoxy)-ethan-1-ol.
 18. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 1-ethyl-2-(2''-methyl-4''-bromophenoxy)-ethan-1-ol.
 19. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said substituted phenyl ether antimicrobial component is 1-methyl-2-(2''-chlorophenoxy)-ethan-1-ol.
 20. Pasty and liquid washing and washing adjuvants consisting of 10 to 60 percent by weight of the antimicrobial washing and washing adjuvant preparations of claim 8 and from 40 to 90 percent by weight of solvents selected from the group consisting of water and water-soluble organic solvents.
 21. Solid washing preparations consisting of from 1 to 70 percent of the antimicrobial washing and washing adjuvants preparations of claim 8 and from 99 to 30 percent by weight of substantially water insoluble mechanical scouring agents selected from the group consisting of quartz flour, marble dust and ground pumice.
 22. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said component (b) includes from 0 to 6 percent by weight of said component (b) of foam stabilizer selected from the group consisting of fatty alcohols and higher alkane terminal diols.
 23. The antimicrobial washing and washing adjuvant preparations of claim 8 wherein said component (b) includes from 0 to 8 percent by weight of said component (b) of nonsurface-active foam inhibitors selected from the group consisting of N-alkylated aminotriazines, chlorinated N-alkylated aminotriazines, paraffins, halogenated paraffins and aliphatic C8 to C20 ketones.
 24. The antimicrobial washing and washing adjuvant preparations of claim 8 having a further content of a minor amount of soil suspension agents.
 25. The antimicrobial washing and washing adjuvant preparations of claim 8 having a further content of a minor amount of optical brighteners. 